U.S. patent number 5,629,376 [Application Number 08/063,211] was granted by the patent office on 1997-05-13 for polyacrylic acid compositions for textile processing.
This patent grant is currently assigned to Peach State Labs, Inc.. Invention is credited to Jeffrey R. Alender, Thomas H. Moss, III, R. Richard Sargent, Michael S. Williams.
United States Patent |
5,629,376 |
Sargent , et al. |
May 13, 1997 |
**Please see images for:
( Certificate of Correction ) ** |
Polyacrylic acid compositions for textile processing
Abstract
Novel polyacrylic acid resins are prepared by polymerizing a
monomer selected from the group consisting of H.sub.2
C.dbd.CHCO.sub.2 X, H.sub.2 C.dbd.CR.sup.1 CO.sub.2 X, HR.sup.2
C.dbd.CHCO.sub.2 X, HR.sup.2 C.dbd.CR.sup.1 CO.sub.2 X, HR.sup.2
C.dbd.CHCOX, H.sub.2 C.dbd.CHCOX, H.sub.2 C.dbd.CR.sup.1 COX,
HR.sup.2 C.dbd.CR.sup.1 COX, H.sub.2 C.dbd.CHCSO.sub.v X, HR.sup.2
C.dbd.CHCSO.sub.v X, HR.sup.2 C.dbd.CR.sup.1 CSO.sub.v X, H.sub.2
C.dbd.CR.sup.1 CSO.sub.v X, H.sub.2 C.dbd.CHCON(R.sup.3).sub.2,
HR.sup.2 C.dbd.CHCON(R.sup.3).sub.2, H.sub.2 C.dbd.CR.sup.1
CON(R.sup.3).sub.2, OR HR.sup.2 C.dbd.CR.sup.1 CON(R.sup.3).sub.2,
or a combination thereof, in the presence of at least 10% by weight
of reaction components of an aromatic sulfonic acid or its salt,
wherein: R.sup.1 and R.sup.2 are independently a substituted or
unsubstituted alkyl, alkenyl, aromatic, aralkyl or alkaryl moiety
of C.sub.1 to C.sub.20 ; R.sup.3 is independently hydrogen or a
substituted or unsubstituted alkyl, alkenyl, aromatic, aralkyl or
alkaryl moiety of C.sub.1 to C.sub.20 ; and X is hydrogen,
substituted or unsubstituted alkyl, alkenyl, aromatic, aralkyl, or
alkaryl moiety of C.sub.1 to C.sub.20 ; --CH.sub.2 CH.sub.2
(CF.sub.2 CF.sub.2).sub.n CF.sub.2 CF.sub.3, wherein n is 1-7;
polyoxyalkylene; --C(R.sup.2).sub.2 R.sup.3 Y, wherein R.sup.3 is
alkylene or polyoxyalkylene (or a combination thereof), and Y is
--OSO.sub.3 H, --SO.sub.3 H, --CO.sub.2 H, --PO.sub.3 H,
--OPO.sub.3 H, or a salt thereof; CF.sub.3 (CF.sub.2).sub.q -,
wherein q is 1-11, hexafluorobutyl, tetrafluoropropyl, sodium,
potassium, lithium, ammonium, or quaternary amine; and v is 0, 1,
or 2.
Inventors: |
Sargent; R. Richard (Rome,
GA), Williams; Michael S. (Rome, GA), Moss, III; Thomas
H. (Rome, GA), Alender; Jeffrey R. (Marietta, GA) |
Assignee: |
Peach State Labs, Inc. (Rome,
GA)
|
Family
ID: |
22047709 |
Appl.
No.: |
08/063,211 |
Filed: |
May 17, 1993 |
Related U.S. Patent Documents
|
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
606467 |
Oct 31, 1990 |
5212272 |
|
|
|
Current U.S.
Class: |
524/745; 526/245;
510/245; 526/317.1; 526/303.1; 526/287; 526/277; 526/328; 510/476;
510/278; 526/225 |
Current CPC
Class: |
C14C
3/22 (20130101); C09K 21/06 (20130101); C11D
3/3757 (20130101); C09K 23/00 (20220101); C09K
15/10 (20130101); C08F 2/44 (20130101); D06P
1/5257 (20130101); D06M 7/00 (20130101); C08F
20/00 (20130101); D06M 15/263 (20130101); C11D
3/378 (20130101); D06M 2200/40 (20130101) |
Current International
Class: |
B01F
17/00 (20060101); C09K 15/10 (20060101); C11D
3/37 (20060101); C09K 21/00 (20060101); C09K
15/00 (20060101); C09K 21/06 (20060101); D06P
1/52 (20060101); C14C 3/22 (20060101); D06P
1/44 (20060101); D06M 15/263 (20060101); C14C
3/00 (20060101); C08F 2/44 (20060101); C08F
20/00 (20060101); D06M 15/21 (20060101); C08K
005/42 (); C11D 001/22 (); C08F 002/00 (); C08F
122/18 (); C08F 130/02 (); C08F 128/02 (); C08F
120/54 () |
Field of
Search: |
;526/225,245,277,287,303.1,317.1,328 ;524/745 ;252/553 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
0118983 |
|
Sep 1984 |
|
EP |
|
0345212 |
|
Dec 1989 |
|
EP |
|
0417960 |
|
Mar 1991 |
|
EP |
|
WO91/14512 |
|
Oct 1991 |
|
WO |
|
WO92/18332 |
|
Oct 1992 |
|
WO |
|
Other References
American Dyestuff Reporter 77(5), 36 (1988). .
Man-Made Fibers, 4th Ed., Heywood Books (1966), pp. 646-651. .
World Abstract, 312 vol. 8(1) 1976/3155. .
World Textile Abstract, vol. 19(6) 1987/1675. .
World Textile Abstract, vol. 19(6) 1987/1678. .
World Textile Abstract, vol. 15(24) 1983/7785. .
World Textile Abstract, vol. 15(20) 1983/6589. .
World Textile Abstract, vol. 15(20) 1983/6590. .
World Textile Abstract, vol. 17(1) 1985/155. .
Chemical Abstract 110:156016k, (1989). .
Chemical Abstract, 111:8831c, (1989). .
Chemical Abstract, 105:210361f, (1986). .
Chemical Abstract, 102:205391z, (1985). .
Chemical Abstract, 92:95595j, (1980). .
Chemical Abstract, 98:199765e, (1983). .
Chemical Abstract, 102:115098e, (1985). .
Chemical Abstract, 80:97290q, (1974). .
Chemical Abstract, 107:116954w, (1987). .
World Textile Abstract, vol. 9(13) 1977/5207. .
World Textile Abstract, vol. 11 1979/3919. .
World Textile Abstract, vol. 7 1975/1304. .
Chemical Abstract, 112:21868k, (1990)..
|
Primary Examiner: Schofer; Joseph L.
Assistant Examiner: Cheng; Wu C.
Attorney, Agent or Firm: Kilpatrick & Cody
Parent Case Text
BACKGROUND OF THE INVENTION
This application is a continuation-in-part application of U.S. Ser.
No. 07/606,467, filed on Oct. 31, 1990 by R. Richard Sargent and
Michael S. Williams, now U.S. Pat. No. 5,212,272.
Claims
We claim:
1. A water soluble polymeric composition prepared by polymerizing a
monomer selected from the group consisting of H.sub.2
C.dbd.CHCO.sub.2 X, H.sub.2 C.dbd.CHR.sup.1 CO.sub.2 X, HR.sup.2
C.dbd.CHCO.sub.2 X, HR.sup.2 C.dbd.CR.sup.1 CO.sub.2 X, HR.sup.2
C.dbd.CHCOX, H.sub.2 C.dbd.CHCOX, H.sub.2 C.dbd.CR.sup.1 COX,
HR.sup.2 C.dbd.CR.sup.1 COX, H.sub.2 C.dbd.CHCON(R.sup.3).sub.2,
HR.sup.2 C.dbd.CHCON(R.sup.3).sub.2, H.sub.2 C.dbd.CR.sup.1
CON(R.sup.3).sub.2, or HR.sup.2 C.dbd.CR.sup.1 CON(R.sup.3).sub.2,
or a combination thereof, in the presence of at least 10% by weight
of reaction components, of an aromatic sulfonic acid or its salt,
wherein:
R.sup.1 and R.sup.2 are independently an alkyl, alkenyl, aromatic,
aralkyl or alkaryl moiety of C.sub.1 to C.sub.20 that is optionally
substituted with one or more halogen; hydroxyl, sulfate, sulfonic
acid, phosphoric acid, or carboxylic acid moieties (or the
corresponding sulfonic, phosphoric or carboxylic acid esters), or a
combination thereof;
R.sup.3 is independently hydrogen or an alkyl, alkenyl, aromatic,
aralkyl or alkaryl moiety of C.sub.1 to C.sub.20 that is optionally
substituted with one or more halogen, hydroxyl, sulfate, sulfonic
acid, phosphoric acid, or carboxylic acid moieties (or the
corresponding sulfonic, phosphoric or carboxylic acid esters), or a
combination thereof; and
X is hydrogen, alkyl, alkenyl, aromatic, aralkyl or alkaryl moiety
of C.sub.1 to C.sub.20 that is optionally substituted with one or
more halogen, hydroxyl, carboxylic acid, phophoric acid, or
sulfonic acid moieties (or the alkyl ester thereof); --CH.sub.2
CH.sub.2 (CF.sub.2 CF.sub.2).sub.n CF.sub.2 CF.sub.3, wherein n is
1-7; polyoxyalkylene; --C(R.sup.2).sub.2 R.sup.3 Y, wherein R.sup.3
is alkylene or polyoxyalkylene (or a combination thereof), and Y is
--OSO.sub.3 H, --SO.sub.3 H, --CO.sub.2 H, --PO.sub.3 H,
--OPO.sub.3 H, or a salt therof, CF.sub.3 (CF.sub.2).sub.q -,
wherein q is 1-11, and specifically including hexafluorobutyl and
tetrafluoropropyl; sodium, potassiu, lithium, ammonium, or
quaternary amine; and
v is 0, 1, or 2.
2. The composition of claim 1, wherein the polyoxyalkylene is
selected from the group consisting of --(CH.sub.2 CH.sub.2 O).sub.m
H, --(CH.sub.2 CH.sub.2 CH.sub.2 O).sub.m H, --(CH.sub.2 CH.sub.2
O).sub.m R.sup.1, and --(CH.sub.2 CH.sub.2 CH.sub.2 O).sub.m
R.sup.1 wherein m is 1-200.
3. The composition of claim 1 wherein a textile processing or
cleansing compound is included in the reaction components.
4. The composition of claim 1 wherein R.sup.1 is methyl.
5. The composition of claim 1 wherein X is hydrogen.
6. The composition of claim 1 wherein mixtures of acrylic acids are
polymerized.
7. The composition of claim 1 wherein the aromatic sulfonic acid is
selected from the group consisting of xylene sulfonic acid, toluene
sulfonic acid, benzene sulfonic acid, cumene sulfonic acid,
dodecylbenzene sulfonic acid, dodecyl diphenyloxide disulfonic
acid, and sulfonated dihydroxydiphenylsulfone.
8. The composition of claim 1, wherein a fluorinated C.sub.3
-C.sub.12 ester of acrylic acid or methacrylic acid is included in
the reaction components.
9. The composition of claim 1, wherein a monomer selected from the
group consisting of CH.sub.2 .dbd.C(H)C(O)NHC(CH.sub.3).sub.2
CH.sub.2 SO.sub.3.sup.- Na.sup.+ and CH.sub.2
.dbd.C(CH.sub.3)C(O)NHCH.sub.2 CH.sub.2 CH.sub.2 SO.sub.3.sup.-
Na.sup.+ is included in the reaction components.
10. The composition of claim 1, wherein HOCH.sub.2 CH.sub.2
R.sub.f, wherein R.sub.f is (CF.sub.2 CF.sub.2).sub.n CF.sub.2
CF.sub.3, and n is 1-7 is included in the reaction components.
11. A water dispersible polymeric composition perpared by
polymerizing a monomer selected from the group consisting of
H.sub.2 C.dbd.CHCO.sub.2 X, H.sub.2 C.dbd.CHR.sup.1 CO.sub.2 X,
HR.sup.2 C.dbd.CHCO.sub.2 X, HR.sup.2 C.dbd.CR.sup.1 CO.sub.2 X,
HR.sup.2 C.dbd.CHCOX, H.sub.2 C.dbd.CHCOX, H.sub.2 C.dbd.CR.sup.1
COX, HR.sup.2 C.dbd.CR.sup.1 COX, H.sub.2
C.dbd.CHCON(R.sup.3).sub.2, HR.sup.2 C.dbd.CHCON(R.sup.3).sub.2,
H.sub.2 C.dbd.CR.sup.1 CON(R.sup.3).sub.2, or HR.sup.2
C.dbd.CR.sup.1 CON(R.sup.3).sub.2, or a combination thereof, in the
presence of at least 10% by weight of reaction components, of an
aromatic sulfonic acid or its salt, wherein:
R.sup.1 and R.sup.2 are independently an alkyl, alkenyl, aromatic,
aralkyl or alkaryl moiety of C.sub.1 to C.sub.20 that is optionally
substituted with one or more halogen; hydroxyl, sulfate, sulfonic
acid, phosphoric acid, or carboxylic acid moieties (or the
corresponding sulfonic, phosphoric or carboxylic acid esters), or a
combination thereof;
R.sup.3 is independently hydrogen or an alkyl, alkenyl, aromatic,
aralkyl or alkaryl moiety of C.sub.1 to C.sub.20 that is optionally
substituted with one or more halogen, hydroxyl, sulfate, sulfonic
acid, phosphoric acid, or carboxylic acid moieties (or the
corresponding sulfonic, phosphoric or carboxylic acid esters), or a
combination thereof; and
X is hydrogen, alkyl, alkenyl, aromatic, aralkyl or alkaryl moiety
of C.sub.1 to C.sub.20 that is optionally substituted with one or
more halogen, hydroxyl, carboxylic acid, phophoric acid, or
sulfonic acid moieties (or the alkyl ester thereof); --CH.sub.2
CH.sub.2 (CF.sub.2 CF.sub.2).sub.n CF.sub.2 CF.sub.3, wherein n is
1-7; polyoxyalkylene; --C(R.sup.2).sub.2 R.sup.3 Y, wherein R.sup.3
is alkylene or polyoxyalkylene (or a combination thereof), and Y is
--OSO.sub.3 H, --SO.sub.3 H, --CO.sub.2 H, --PO.sub.3 H,
--OPO.sub.3 H, or a salt therof; CF.sub.3 (CF.sub.2).sub.q -,
wherein q is 1-11, and specifically including hexafluorobutyl and
tetrafluoropropyl; sodium, potassiu, lithium, ammonium, or
quaternary amine; and
v is 0, 1, or 2.
12. A water dispersible polymeric composition prepared by
polymerizing a monomer selected from the group consisting of
H.sub.2 C.dbd.CHCO.sub.2 X, HR.sup.2 C.dbd.CHCO.sub.2 X, or a
combination thereof, in the presence of at least 10% by weight of
reaction components, of an aromatic sulfonic acid or its salt,
wherein:
R.sup.1 and R.sup.2 are independently an aliphatic or aromatic,
moiety of C.sub.1 to C.sub.20 that is optionally substituted with
one or more halogen or sulfonic acid; and
X is hydrogen, aliphatic or aromatic moiety of C.sub.1 or C.sub.10
that is optionally substituted with one or more halogen, hydroxyl,
or sulfonic acid moieties; sodium, potassium or ammonium.
13. The composition of claim 12, wherein R.sup.1 is methyl.
14. The composition of claim 12, wherein X is hydrogen.
15. The composition of claim 12, wherein mixtures of acrylic acids
are polymerized.
16. A water soluble polymeric composition prepared by polymerizing
a monomer selected from the group consisting of H.sub.2
C.dbd.CHCO.sub.2 X, HR.sup.2 C.dbd.CHCO.sub.2 X, or a combination
thereof, in the presence of at least 10% by weight of reaction
components, of an aromatic sulfonic acid or its salt, wherein:
R.sup.1 and R.sup.2 are independently an aliphatic or aromatic,
moiety of C.sub.1 to C.sub.20 that is optionally substituted with
one or more halogen or sulfonic acid; and
X is hydrogen, aliphatic or aromatic moiety of C.sub.1 or C.sub.10
that is optionally substituted with one or more halogen, hydroxyl,
or sulfonic acid moieties; sodium, potassium or ammonium.
17. The composition of claim 16, wherein R.sup.1 is methyl.
18. The composition of claim 16, wherein X is hydrogen.
19. The composition of claim 16, wherein mixtures of acrylic acids
are polymerized.
20. A water dispersible polymeric composition prepared by
polymerizing a monomer selected from the group consisting of
H.sub.2 C.dbd.CR.sup.1 CO.sub.2 X, in the presence of at least 10%
by weight of reaction components, of an aromatic sulfonic acid or
its salt, wherein:
R.sup.1 is selected from ethyl, propyl, isopropyl, butyl, isobutyl,
t-butyl, pentyl, cyclopentyl, ispentyl, neopentyl,
2,2-dimethylbutyl, 2,3-dimethylbutyl, 2-ethylhexyl, octyl, decyl,
dodecyl, stearyl, alkenyl, aromatic, aralkyl or alkaryl moiety of
C.sub.1 to C.sub.20 that is optionally substituted with one or more
halogen; hydroxyl, sulfate, sulfonic acid, phosphoric acid, or
carboxylic acid moieties (or the corresponding sulfonic, phosphoric
or carboxylic acid esters), or a combination thereof;
R.sup.3 is independently hydrogen or an alkyl, alkenyl, aromatic,
aralkyl or alkaryl moiety of C.sub.1 to C.sub.20 that is optionally
substituted with one or more halogen, hydroxyl, sulfate, sulfonic
acid, phosphoric acid, or carboxylic acid moieties (or the
corresponding sulfonic, phosphoric or carboxylic acid esters), or a
combination thereof; and
X is hydrogen, alkyl, alkenyl, aromatic, aralkyl or alkaryl moiety
of C.sub.1 or C.sub.20 that is optionally substituted with one or
more halogen, hydroxyl, carboxylic acid, phosphoric acid, or
sulfonic acid moieties (or the alkyl ester thereof); --CH.sub.2
CH.sub.2 (CF.sub.2 CF.sub.2).sub.n CF.sub.2 CF.sub.3, wherein n is
1-7; polyoxyalkylene; --C(R.sup.2).sub.2 R.sup.3 Y, wherein R.sup.3
is alkylene or polyoxyalkylene (or a combination thereof), and Y is
--OSO.sub.3 H, --SO.sub.3 H, --CO.sub.2 H, --PO.sub.3 H,
--OPO.sub.3 H, or a salt thereof; CF.sub.3 (CF.sub.2).sub.q -,
wherein q is 1-11, and specifically including hexafluorobutyl and
tetrafluoropropyl; sodium, potassium, lithium, ammonium, or
quaternary amine; and
v is 0, 1, or 2.
21. A water soluble polymeric composition prepared by polymerizing
a monomer selected from the group consisting of H.sub.2
C.dbd.CR.sup.1 CO.sub.2 X, in the presence of at least 10% by
weight of reaction components, of an aromatic sulfonic acid or its
salt, wherein:
R.sup.1 is selected from ethyl, propyl, isopropyl, butyl, isobutyl,
t-butyl, pentyl, cyclopentyl, ispentyl, neopentyl,
2,2-dimethylbutyl, 2,3-dimethylbutyl, 2-ethylhexyl, octyl, decyl,
dodecyl, stearyl, alkenyl, aromatic, aralkyl or alkaryl moiety of
C.sub.1 to C.sub.20 that is optionally substituted with one or more
halogen; hydroxyl, sulfate, sulfonic acid, phosphoric acid, or
carboxylic acid moieties (or the corresponding sulfonic, phosphoric
or carboxylic acid esters), or a combination thereof;
R.sup.3 is independently hydrogen or an alkyl, alkenyl, aromatic,
aralkyl or alkaryl moiety of C.sub.1 to C.sub.20 that is optionally
substituted with one or more halogen, hydroxyl, sulfate, sulfonic
acid, phosphoric acid, or carboxylic acid moieties (or the
corresponding sulfonic, phosphoric or carboxylic acid esters), or a
combination thereof; and
X is hydrogen, alkyl, alkenyl, aromatic, aralkyl or alkaryl moiety
of C.sub.1 or C.sub.20 that is optionally substituted with one or
more halogen, hydroxyl, carboxylic acid, phosphoric acid, or
sulfonic acid moieties (or the alkyl ester thereof); --CH.sub.2
CH.sub.2 (CF.sub.2 CF.sub.2).sub.n CF.sub.2 CF.sub.3, wherein n is
1-7; polyoxyalkylene; --C(R.sup.2).sub.2 R.sup.3 Y, wherein R.sup.3
is alkylene or polyoxyalkylene (or a combination thereof), and Y is
--OSO.sub.3 H, --SO.sub.3 H, --CO.sub.2 H, --PO.sub.3 H,
--OPO.sub.3 H, or a salt thereof; CF.sub.3 (CF.sub.2).sub.q -,
wherein q is 1-11, and specifically including hexafluorobutyl and
tetrafluoropropyl; sodium, potassium, lithium, ammonium, or
quaternary amine; and
v is 0, 1, or 2.
22. The composition of claim 1, wherein a monomer of the formula
CH.sub.2 .dbd.C(H or CH.sub.3)COOCH.sub.2 CH.sub.2 R.sub.f, is
included in the reaction components, wherein R.sub.f is CF.sub.3
CF.sub.2 (CF.sub.2 CF.sub.2).sub.n, and n=1-7.
23. The composition of claim 1, wherein CH.sub.2 .dbd.C(H or
CH.sub.3)(COOZ) is included in the reaction components, wherein Z
is selected from the group consisting of --(CH.sub.2 CH.sub.2
O).sub.m H, --(CH.sub.2 CH.sub.2 CH.sub.2 O).sub.m H, --(CH.sub.2
CH.sub.2 O).sub.m R.sup.1, and --(CH.sub.2 CH.sub.2 CH.sub.2
O).sub.m R.sup.1, and m is 1-200.
Description
This invention is in the area of polymer chemistry, and in
particular relates to a group of novel polyacrylic acid derivatives
that can be used in a variety of applications, including textile
applications, and as coatings for hard and soft surfaces, including
paper, wood, and stone.
Polymethacrylic acid and polyacrylic acid, as well as their
copolymers, are important polyelectrolytes that are widely used in
industry for a number of applications, including as thickening
agents for paints, suspending agents for inorganic pigments,
flocculants in metal ore recovery, and in ion-exchange resins,
coatings and dispersants. For example, U.S. Pat. No. 4,043,965 to
Dickson describes a copolymer of acrylic acid and
1,1-dihydroperfluorooctyl methacrylate that is useful as a
soil-release finish in the rinse cycle of a home laundry process.
U.S. Pat. No. 4,680,128 to Portnoy discloses low molecular weight
copolymers of acrylic acid and salts of vinylsulfonic acid for use
as dispersants and deflocculants.
Polymethacrylic acid and a number of copolymers and blends thereof
have been used increasingly to impart stain resistance to nylon
(polyamide) fibers. The anionic moieties of the polymers ionically
bind to protonated terminal amines in the polyamide, blocking
subsequent ionic bonding by anionically charged dyes. U.S. Pat. No.
4,937,123 to Chang, et al., assigned to Minnesota Mining and
Manufacturing Company, describes the use of polymethacrylic acid
and copolymers of methacrylic acid with other ethylenically
unsaturated monomers to impart stain resistant properties to nylon
fibers. U.S. Pat. No. 4,822,373 to Olson, also assigned to
Minnesota Mining and Manufacturing Company, describes a stain
resistant composition prepared by blending a partially sulfonated
novolak resin with a polymethacrylic acid, or a copolymer of
methacrylic acid with ethylenically unsaturated monomers. U.S. Pat.
No. 4,940,757 to Moss, et al., assigned to Peach State Labs, Inc.,
describes a stain resistant polymeric composition that includes a
polymer prepared by polymerizing an .alpha.-substituted acrylic
acid in the presence of a sulfonated formaldehyde condensation
polymer (a novoloid resin) to form a polymeric composition. The
composition has superior stain resist properties over a mere blend
of a poly(.alpha.-substituted acrylic acid) and a novoloid resin as
described in '373 to Olson.
A number of chemical agents other than stain resist agents are
required during textile processing and handling. Examples include
dye levelers, acids to adjust Ph, cleaning agents (detergents,
shampoos, and surfactants), emulsifiers, yarn lubricants,
defoamers, antistatic agents, flame retardants, ultra-violet
absorbing agents, and finishing resins. A substantial amount of the
agents currently used typically remain in the wastewater after use,
increasing the B.O.D. (biological oxygen demand) and C.O.D. (carbon
oxygen demand) of the wastewater. The agents also increase the
hazardous nature of the wastewater, which significantly increases
the burden of water purification placed on the company and on the
publicly owned treatment facilities.
For many textile applications, a textile processing solution is
desired that is in the form of an aqueous solution or an aqueous
stable dispersion. U.S. Pat. No. 2,639,279 to Caldwell discloses a
method for the precipitation polymerization of unsaturated
monomers, wherein the unsaturated monomers are polymerized in an
aqueous solution of an alkali metal salt of an aromatic sulfonic
acid of the benzene series. The patent teaches that while the
monomers are soluble in the aqueous solution of an alkali metal
salt of the aromatic sulfonic acid, the polymer prepared from the
process falls out of the solution as a granular precipitate. The
precipitate is separated, purified, and washed with water. The
patent does not teach how to prepare water soluble solutions or
water stable dispersions of polymeric compositions that would be
suitable for use in textile applications.
It would also be of significant environmental benefit to develop
textile processing chemicals that adhere to the textile fiber (that
would be exhausted onto the fiber) instead of remaining in the
wastewater to be removed later at significant expense. It would be
of even greater value to have an exhaustible processing chemical
that improves the properties of the textile fiber for residential
or commercial use.
It is therefore an object of the present invention to provide
textile processing and handling agents that have improved
performance over the currently used agents.
It is another object of the present invention to provide processing
chemicals for textile applications that are exhausted onto
synthetic and natural fibers and substrates.
It is still another object of the present invention to provide an
exhaustible processing chemical that improves the properties of the
synthetic and natural fibers and substrates.
It is still another object of the present invention to provide
water soluble polymeric solutions and water stable polymeric
dispersions for textile processing.
It is another object of the present invention to provide new
acrylic-based coatings for hard and soft surfaces, including paper,
wood, stone, concrete, brick, masonry, glass, ceramic, porcelain,
hard plastics and rubbers, marble, granite, other architectural
building materials, metals, and composites.
SUMMARY OF THE INVENTION
New polyacrylic acid based resins are prepared by polymerizing
H.sub.2 C.dbd.CHCO.sub.2 X, H.sub.2 C.dbd.CR.sup.1 CO.sub.2 X,
HR.sup.2 C.dbd.CHCO.sub.2 X, HR.sup.2 C.dbd.CR.sup.1 CO.sub.2 X,
HR.sup.2 C.dbd.CHCOX, H.sub.2 C.dbd.CHCOX, H.sub.2 C.dbd.CR.sup.1
COX, HR.sup.2 C.dbd.CR.sup.1 COX, H.sub.2 C.dbd.CHCSO.sub.v X,
HR.sup.2 C.dbd.CHCSO.sub.v X, HR.sup.2 C.dbd.CR.sup.1 CSO.sub.v X,
H.sub.2 C.dbd.CR.sup.1 CSO.sub.v X, H.sub.2
C.dbd.CHCON(R.sup.3).sub.2, HR.sup.2 C.dbd.CHCON(R.sup.3).sub.2,
H.sub.2 C.dbd.CR.sup.1 CON(R.sup.3).sub.2, or HR.sup.2
C.dbd.CR.sup.1 CON(R.sup.3).sub.2, or a combination thereof, in the
presence of an aromatic sulfonic acid or its salt, wherein:
R.sup.1 and R.sup.2 are independently an alkyl, alkenyl, aromatic,
aralkyl or alkaryl moiety of C.sub.1 to C.sub.20 that is optionally
substituted with one or more halogen; hydroxyl, sulfate, sulfonic
acid, phosphoric acid, or carboxylic acid moieties (or the
corresponding sulfonic, phosphoric or carboxylic acid esters), or a
combination thereof;
R.sup.3 is independently hydrogen or an alkyl, alkenyl, aromatic,
aralkyl or alkaryl moiety of C.sub.1 to C.sub.20 that is optionally
substituted with one or more halogen, hydroxyl, sulfate, sulfonic
acid, phosphoric acid, or carboxylic acid moieties (or the
corresponding sulfonic, phosphoric or carboxylic acid esters), or a
combination thereof; and
X is hydrogen, alkyl, alkenyl, aromatic, aralkyl or alkaryl moiety
of C.sub.1 to C.sub.20 that is optionally substituted with one or
more halogen, hydroxyl, carboxylic acid, phosphoric acid, or
sulfonic acid moieties (or the alkyl ester thereof); --CH.sub.2
CH.sub.2 (CF.sub.2 CF.sub.2).sub.n CF.sub.2 CF.sub.3, wherein n is
1-7; polyoxyalkylene, including but not limited to --(CH.sub.2
CH.sub.2 O).sub.m H, --(CH.sub.2 CH.sub.2 CH.sub.2 O).sub.m H,
--(CH.sub.2 CH.sub.2 O).sub.m R.sup.1, or --(CH.sub.2 CH.sub.2
CH.sub.2 O).sub.m R.sup.1 wherein m is 1-200; --C(R.sup.2).sub.2
R.sup.3 Y, wherein R.sup.3 is alkylene or polyoxyalkylene (or a
combination thereof), and Y is --OSO.sub.3 H, --SO.sub.3 H,
--CO.sub.2 H, --PO.sub.3 H, --OPO.sub.3 H, or a salt thereof;
CF.sub.3 (CF.sub.2).sub.q - wherein q is 1-11, hexafluorobutyl,
tetrafluoropropyl; sodium, potassium, lithium, ammonium, or
quaternary amine; and
v is 0, 1, or 2.
In a second embodiment, a textile processing or cleansing compound
is included in the polymerization reaction, along with the acrylic
acid or acrylic acid derivative and sulfonated aromatic
compound.
The polymerization reaction components are selected based on the
desired properties of the resulting polymeric product for a
specific application. The choice of aromatic sulfonic acid or its
salt and textile processing or cleansing agent will influence the
aqueous solubility, wettability, ionic character, surfactant
capability, exhaustibility, soil and grease absorption, chelation
ability, flame retardancy, and detergency of the polymer.
Water soluble and water dispersible polymeric compositions for
textile processing can be prepared by the appropriate selection of
acrylic acid derivative monomers and aromatic sulfonic acid.
The resulting polymers have superior properties for use in textile
processing and cleaning, and can be used as detergents, dye
levelers, soil resist agents, surfactants, emulsifiers, yarn
lubricants, copolymerizing agents, polymer after treat agents,
finishing agents, leather tanning and finishing auxiliaries,
defoamers, chelating agents, flocculants, anti-static agents, flame
retardants, metal cleaners, metal coatings, and as multipurpose
acids (replacing or supplementing, for example, phosphoric, acetic,
formic, sulfonic, or sulfamic acid in a processing procedure).
The polymeric compositions disclosed herein can also be used
generally as coatings for hard or soft surfaces, including wood,
paper, stone, concrete, brick, masonery, glass, ceramic, porcelain,
hard plastics and rubbers, marble, granite, other architectural
building materials, metals, and composites.
DETAILED DESCRIPTION OF THE INVENTION
The term alkyl, as used herein, unless otherwise specified, refers
to a saturated straight, branched, or cyclic hydrocarbon of C.sub.1
to C.sub.20, and specifically includes methyl, ethyl, propyl,
isopropyl, butyl, isobutyl, t-butyl, pentyl, cyclopentyl,
isopentyl, neopentyl, hexyl, isohexyl, cyclohexyl, 3-methylpentyl,
2,2-dimethylbutyl, 2,3-dimethylbutyl, and 2-ethylhexyl, octyl,
decyl, dodecyl, and stearyl.
The term alkylene, as used herein, and unless otherwise defined,
refers to a divalent alkyl group of from C.sub.1 to C.sub.20.
The term alkenyl, as referred to herein, and unless otherwise
specified, refers to a straight, branched, or cyclic (in the case
of C.sub.5-6) hydrocarbon of C.sub.2 to C.sub.20 with at least one
double bond.
The term aliphatic refers to alkyl and alkenyl moieties.
The term aryl or aromatic, as used herein, and unless otherwise
specified, refers to phenyl, substituted phenyl, naphthyl, or
substituted naphthyl, wherein the substituent is halo, alkyl,
hydroxyl, carboxyl, sulfonyl, or phosphoric acid, and wherein the
aromatic ring can have 1, 2, 3, or 4 substituents.
The term halo, as used herein, includes fluoro, chloro, bromo, and
iodo.
The term aralkyl refers to an aryl group with an alkyl
substituent.
The term alkaryl refers to an alkyl group that has an aryl
substituent.
The term polyoxyalkylene refers to a moiety that has a repeating
unit of -(alkylene-O)-, wherein alkylene is a divalent alkyl group.
Preferred alkylene groups in the polyoxyalkene are methylene,
ethylene and propylene. The polyoxyalkylene can be terminated with
a wide variety of moieties, including hydrogen and alkyl, for
example, CH.sub.3 (CH.sub.2).sub.n, wherein n is 0-30.
The term aromatic sulfonic acid or sulfonated aromatic compound
refers to any aromatic compound in which a sulfonic acid group is
covalently bound to an aromatic moiety, and for the purpose of this
invention, does not include aromatic sulfonic acids with ethylenic
unsaturation, for example, sulfonated styrene.
As used herein, the term polyacrylic acid includes polymers
prepared by the polymerization of H.sub.2 C.dbd.CHCO.sub.2 X,
H.sub.2 C.dbd.CR.sup.1 CO.sub.2 X, HR.sup.2 C.dbd.CHCO.sub.2 X,
HR.sup.2 C.dbd.CR.sup.1 CO.sub.2 X, HR.sup.2 C.dbd.CHCOX, H.sub.2
C.dbd.CHCOX, H.sub.2 C.dbd.CR.sup.1 COX, H.sup.2 C.dbd.CR.sup.1
COX, H.sub.2 C.dbd.CHCSO.sub.v X, HR.sup.2 C.dbd.CHCSO.sub.v X,
HR.sup.2 C.dbd.CR.sup.1 CSO.sub.v X, H.sub.2 C.dbd.CR.sup.1
CSO.sub.v X, H.sub.2 C.dbd.CHCON(R.sup.3).sub.2, HR.sup.2
C.dbd.CHCON(R.sup.3).sub.2, H.sub.2 C.dbd.CR.sup.1
CON(R.sup.3).sub.2, or HR.sup.2 C.dbd.CR.sup.1 CON(R.sup.3).sub.2,
with X and R as defined above.
The term acrylic acid derivative, as used herein includes H.sub.2
C.dbd.CHCO.sub.2 X, H.sub.2 C.dbd.CR.sup.1 CO.sub.2 X, HR.sup.2
C.dbd.CHCO.sub.2 X, HR.sup.2 C.dbd.CR.sup.1 CO.sub.2 X, HR.sup.2
C.dbd.CHCOX, H.sub.2 C.dbd.CHCOX, H.sub.2 C.dbd.CR.sup.1 COX,
HR.sup.2 C.dbd.CR.sup.1 COX, H.sub.2 C.dbd.CHCSO.sub.v X, HR.sup.2
C.dbd.CHCSO.sub.v X, HR.sup.2 C.dbd.CR.sup.1 CSO.sub.v X, H.sub.2
C.dbd.CR.sup.1 CSO.sub.v X, H.sub.2 C.dbd.CHCON(R.sup.3).sub.2,
HR.sup.2 C.dbd.CHCON(R.sup.3).sub.2, H.sub.2 C.dbd.CR.sup.1
CON(R.sup.3).sub.2, or HR.sup.2 C.dbd.CR.sup.1 CON(R.sup.3).sub.2,
with X and R as defined above.
Textile processing terms, as used herein, are defined as follows.
Acid dye levelers are compounds that allow uniform distribution of
a dye during the coloring process. If a leveler is not used, the
dyestuff tends to adhere in a nonuniform fashion, causing blotching
of the color and Barre'. Textile processing acids are compounds
used to adjust the pH during dyebath and finishing treatments.
Surfactants and emulsifiers are surface active agents that modify
the surface energy between two liquid phases. A yarn lubricant is
an oil or emulsion finish that is applied to a fiber to prevent
damage to the fiber during textile processing or applied to
knitting yarns to make them more pliable. A defoamer is a chemical
that reduces the foamability of a solution. An antistatic agent is
a reagent capable of preventing, reducing, or dissipating static
electrical charge that is produced on materials. A flame retardant
is a chemical that is incorporated into a textile fiber during
manufacture or use to reduce flammability. Ultra-violet absorbers
are chemicals that absorb ultra-violet radiation, and are used to
protect the fiber from damage caused by uv absorption. A finishing
agent is a chemical applied to a substrate for dimensional
stability and other desired aesthetic effects.
In a preferred embodiment, acrylic acid based polymeric
compositions are disclosed that are prepared by polymerizing
H.sub.2 C.dbd.CHCO.sub.2 X, H.sub.2 C.dbd.CR.sup.1 CO.sub.2 X,
HR.sup.2 C.dbd.CHCO.sub.2 X, HR.sup.2 C.dbd.CR.sup.1 CO.sub.2 X,
HR.sup.2 C.dbd.CHCOX, H.sub.2 C.dbd.CHCOX, H.sub.2 C.dbd.CR.sup.1
COX, HR.sup.2 C.dbd.CR.sup.1 COX, H.sub.2 C.dbd.CHCSO.sub.v X,
HR.sup.2 C.dbd.CHCSO.sub.v X, HR.sup.2 C.dbd.CR.sup.1 CSO.sub.v X,
H.sub.2 C.dbd.CR.sup.1 CSO.sub.v X, H.sub.2
C.dbd.CHCON(R.sup.3).sub.2, HR.sup.2 C.dbd.CHCON(R.sup.3).sub.2,
H.sub.2 C.dbd.CR.sup.1 CON(R.sup.3).sub.2, or HR.sup.2
C.dbd.CR.sup.1 CON(R.sup.3).sub.2, with X and R as defined above,
or a combination thereof, in the presence of at least 10% by weight
of the reaction components of an aromatic sulfonic acid or its
salt, or a mixture of aromatic sulfonic acids.
An important advantage of the polymers described herein is that
they can replace current textile processing and finishing chemicals
that can have an unfavorable effect on the environment. For
example, laundry detergents now commonly include phosphoric acid
salts or their esters as surfactants. These compounds are very
difficult to remove from wastewater and are often released into
fresh water, where they accelerate the aging of rivers, streams,
and lakes. In certain countries, phosphoric acid esters are being
replaced with acrylic and methacrylic acid polymers. An alternative
laundry detergent can be prepared as described herein by
polymerizing an acrylic acid in the presence of a sulfonated
aromatic compound and a phosphoric acid ester. The resulting
laundry detergent retains the advantages of the phosphoric acid
ester but is easily removed from wastewater using conventional
wastewater treatment processes.
The polymers described herein can also be used in fiber finishing
processes to replace or supplement the acid dye levelers, soil
resist agents, surfactants, emulsifiers, and acids for pH
adjustment that are now used. These compounds are eliminated in the
waste stream, significantly increasing the biological oxygen demand
(B.O.D.) and the chemical oxygen demand (C.O.D.) of the wastewater.
The polymers described herein can be exhausted onto nylon fiber,
wool, silk, or leather, so that they are not eliminated in the
waste stream, thereby decreasing the B.O.D. and C.O.D. of the
wastewater, and at the same time actually improving the physical
properties and durability of the fiber.
The polymeric composition prepared using this method can optionally
be provided as a salt. Nonlimiting examples are (a) base addition
salts formed with metal cations such as sodium, potassium, zinc,
calcium, magnesium, aluminum, and the like, or salts formed with
nitrogenous compounds such as ammonium ion, quaternary amine, or
ethylenediamine; or (b) acid addition salts formed with inorganic
acids (for example, hydrochloric acid, hydrobromic acid, sulfuric
acid, phosphoric acid, nitric acid, and the like); and salts formed
with organic acids such as acetic acid, oxalic acid, tartaric acid,
succinic acid, malic acid, ascorbic acid, benzoic acid, tannic
acid, pamoic acid, alginic acid, polyglutamic acid, or aromatic
sulfonic acids; or (c) combinations of (a) and (b).
The acrylic acid derivatives can be copolymerized with other
ethylenic unsaturated monomers in the presence of the aromatic
sulfonic acid. Such monomers include, for example, unsaturated
monocarboxylic acids, unsaturated polycarboxylic acids and
anhydrides; unsaturated substituted and unsubstituted esters and
amides of carboxylic acids and anhydrides; nitriles; vinyl
monomers; vinylidene monomers; monoolefinic and polyolefinic
monomers; and unsaturated heterocyclic monomers.
Representative monomers include, for example, acrylic acid, H.sub.2
C.dbd.CHC(O)NH(alkyl)SO.sub.3.sup.- Na.sup.+, itaconic acid,
citraconic acid, aconitic acid, maleic acid, maleic anhydride,
fumaric acid, crotonic acid, cinnamic acid, oleic acid, palmitic
acid, vinyl sulfonic acid, vinyl phosphonic acid, alkyl or
cycloalkyl esters of the foregoing acids, the alkyl or cycloalkyl
groups having 1 to 18 carbon atoms such as, for example, ethyl,
butyl, 2-ethylhexyl, octadecyl, 2-sulfoethyl, acetoxyethyl,
cyanoethyl, hydroxyethyl and hydroxypropyl acrylates and
methacrylates, and amides of the foregoing acids, such as, for
example, acrylamide, methacrylamide, methylolacrylamide, and
1,1-dimethylsulfoethylacrylamide, acrylonitrile, methacrylonitrile,
styrene, .alpha.-methylstyrene, p-hydroxystyrene, chlorostyrene,
sulfostyrene, vinyl alcohol, N-vinyl pyrrolidone, vinyl acetate,
vinyl chloride, vinyl ethers, vinyl sulfides, vinyl toluene,
butadiene, isoprene, chloroprene, ethylene, isobutylene, vinylidene
chloride, sulfated castor oil, sulfated sperm oil, sulfated soybean
oil, and sulfonated dehydrated castor oil, and sulfonated marine
oil. Particularly useful monomers include, for example, alkyl
acrylates having 1-4 carbon atoms, itaconic acid, sodium
sulfostyrene, and sulfated castor oil. Mixtures of the monomers,
such as, for example, sodium sulfostyrene and styrene, and sulfated
castor oil and acrylic acid, can be copolymerized with the
methacrylic acid.
Methods to polymerize a monomer in the presence of a polymer are
described in a number of sources, including U.S. Pat. No. 4,940,757
to Moss, incorporated by reference herein.
I. (.alpha. or .beta.)-Substituted Acrylic Acid or Acrylic Acid
The polyacrylic acid resin is prepared by polymerizing H.sub.2
C.dbd.CHCO.sub.2 X, H.sub.2 C.dbd.CR.sup.1 CO.sub.2 X, HR.sup.2
C.dbd.CHCO.sub.2 X, HR.sup.2 C.dbd.CR.sup.1 CO.sub.2 X, HR.sup.2
C.dbd.CHCOX, H.sub.2 C.dbd.CHCOX, H.sub.2 C.dbd.CR.sup.1 COX,
HR.sup.2 C.dbd.CR.sup.1 COX, H.sub.2 C.dbd.CHCSO.sub.v X, HR.sup.2
C.dbd.CHCSO.sub.v X, HR.sup.2 C.dbd.CR.sup.1 CSO.sub.v X, H.sub.2
C.dbd.CR.sup.1 CSO.sub.v X, H.sub.2 C.dbd.CHCON(R.sup.3).sub.2,
HR.sup.2 C.dbd.CHCON(R.sup.3).sub.2, H.sub.2 C.dbd.CR.sup.1
CON(R.sup.3).sub.2, or HR.sup.2 C.dbd.CR.sup.1 CON(R.sup.3).sub.2,
or a combination thereof, in the presence of an aromatic sulfonic
acid or its salt, wherein:
R.sup.1 and R.sup.2 are independently an alkyl, alkenyl, aromatic,
aralkyl or alkaryl moiety of C.sub.1 to C.sub.20 that is optionally
substituted with one or more halogen; hydroxyl, sulfate, sulfonic
acid, phosphoric acid, or carboxylic acid moieties (or the
corresponding sulfonic, phosphoric or carboxylic acid esters), or a
combination thereof;
R.sup.3 is independently hydrogen or an alkyl, alkenyl, aromatic,
aralkyl or alkaryl moiety of C.sub.1 to C.sub.20 that is optionally
substituted with one or more halogen, hydroxyl, sulfate, sulfonic
acid, phosphoric acid, or carboxylic acid moieties (or the
corresponding sulfonic, phosphoric or carboxylic acid esters), or a
combination thereof; and
X is hydrogen, alkyl, alkenyl, aromatic, aralkyl or alkaryl moiety
of C.sub.1 to C.sub.20 that is optionally substituted with one or
more halogen, hydroxyl, carboxylic acid, phosphoric acid, or
sulfonic acid moieties (or the alkyl ester thereof); --CH.sub.2
CH.sub.2 (CF.sub.2 CF.sub.2).sub.n CF.sub.2 CF.sub.3, wherein n is
1-7; polyoxyalkylene, including but not limited to --(CH.sub.2
CH.sub.2 O).sub.m H, --(CH.sub.2 CH.sub.2 CH.sub.2 O).sub.m H,
--(CH.sub.2 CH.sub.2 O).sub.m R, or --(CH.sub.2 CH.sub.2 CH.sub.2
O).sub.m R wherein m is 1-200; --C(R.sup.2).sub.2 R.sup.3 Y,
wherein R.sup.3 is alkylene or polyoxyalkylene (or a combination
thereof), and Y is --OSO.sub.3 H, --SO.sub.3 H, --CO.sub.2 H,
--PO.sub.3 H, --OPO.sub.3 H, or a salt thereof; CF.sub.3
(CF.sub.2).sub.q - or C.sub.3 (CF.sub.2).sub.q -, wherein q is
1-11, and specifically including hexafluorobutyl and
tetrafluoropropyl; sodium, potassium, lithium, ammonium, or
quaternary amine; and
v is 0, 1, or 2.
Mixtures of acrylic acid derivatives can also be reacted together.
Esters of substituted acrylic acids can be polymerized in
combination with unesterified substituted acrylic acids. If the
alcohol from which the ester is prepared is hydrophobic, as the
percentage of ester in the composition increases, water solubility
and affinity for the polyamide fiber will decrease. If the alcohol
from which the ester is prepared is hydrophilic or basic, water
solubility is not adversely affected or is improved. Acrylic acid
derivatives with low water solubility can be polymerized using
emulsion polymerization techniques known to those skilled in the
art.
In an alternative embodiment, an unhalogenated acrylic acid
derivative, or acrylic acid, is copolymerized with a partially
halogenated or perhalogenated acrylic acid or acrylate. A
particularly useful monomer is CH.sub.2 .dbd.C[H or CH.sub.3 ]
[(C(O)OCH.sub.2 CH.sub.2 R.sub.f ], wherein R.sub.f is CF.sub.3
CF.sub.2 (CF.sub.2 CF.sub.2)n, and n=1-7. Monomers of this class
are often sold as a mixture that contains a range of chain lengths
in the R.sub.f moiety.
In another embodiment, fluorinated C.sub.3 -C.sub.12 esters of
acrylic acids are polymerized or copolymerized in the presence of
the aromatic sulfonic acid. It is preferable for textile
applications to copolymerize a fluorinated acrylate with at least
some free acrylic acid. Fluorinated alkyl esters of acrylic acid
have low water solubility. When polymerizing or copolymerizing
these esters, an emulsifying agent such as a nonyl phenol, an
ethoxylated oleic acid ester, or a sorbitan monooleate can be
included in the reaction mixture.
It is sometimes desirable to include an alkyl acrylate or alkyl
methacrylate in the polymerization reaction. The inclusion of these
monomers in the polymerization reaction appears to assist in the
formation of random, as opposed to block, copolymers. One example
of a class of alkyl acrylates that is useful is CH.sub.2 .dbd.C[H
or CH.sub.3 ] [(C(O)OZ], wherein Z is a polyoxyalkylene, including
but not limited to --(CH.sub.2 CH.sub.2 O).sub.m H, --(CH.sub.2
CH.sub.2 CH.sub.2 O).sub.m H, --(CH.sub.2 CH.sub.2 O).sub.m
R.sup.1, or --(CH.sub.2 CH.sub.2 CH.sub.2 O).sub.m R.sup.1 wherein
m is 1-200.
It is often desired that textile processing agents be water soluble
or water dispersible. One of ordinary skill in the art of acrylic
acid polymerizations can easily choose a monomer mix, aromatic
sulfonic acid, and optionally, textile processing compounds, that
will provide a water soluble polymeric composition or a water
stable polymeric dispersion. The term water soluble, as used
herein, refers to a material that is soluble to the extent of at
least approximately 10, and preferably, 15 or 20, grams per liter
of water. The term water stable dispersion, as used herein, refers
to a material that remains dispersed in water to the extent of at
least approximately 10, and preferably, 15 or 20, grams per liter
of water for a period of at least approximately 1 week at ambient
temperature.
Water solubility or dispersibility can be enhanced by including an
appropriate amount of a monomer in the polymerization reaction that
contains free carboxylic acid, sulfonic acid, or phosphoric acid,
or a salt thereof. One example is CH.sub.2 .dbd.C[H or CH.sub.3 ]
[(C(O)OC(R.sup.2).sub.2 R.sup.3 Y], wherein R.sup.3 is alkylene or
polyoxyalkylene, and Y is --SO.sub.3 H, --CO.sub.2 H, or --PO.sub.4
H, or a salt thereof. Other examples include CH.sub.2
.dbd.C(H)C(O)NHC(CH.sub.3).sub.2 CH.sub.2 SO.sub.3.sup.- Na.sup.+
and CH.sub.2 .dbd.C(CH.sub.3)C(O)NHCH.sub.2 CH.sub.2 CH.sub.2
SO.sub.3.sup.- Na.sup.+.
If a portion of the acrylic acid derivatives used in the
polymerization reaction does not include a free carboxylic acid,
sulfonic acid, or phosphoric acid, or a salt thereof, an
appropriate portion of the monomers should contain other
hydrophilic moieties to impart adequate water solubility or
dispersability to the polymer, including but not limited to
hydroxyl and sulfonamide. Water solubility or dispersibility can
also be enhanced by the proper choice of initiating agent. In
general, persulfates increase both water solubility and
dispersibility.
It is desirable to include an alpha-substituted acrylic acid, and
in particular, methacrylic acid, in polymeric composition for use
as acid dye levelers and soil resist agents. These monomers
increase to substantivity of the polymeric composition for the
fiber. They also increase the hardness of the polymer film on the
fiber.
II. Aromatic Sulfonic Acids and their Salts
Aromatic sulfonic acids are included in the acrylic acid
polymerization reaction to impart a number of characteristics to
the polymer, including, but not limited to, anionic character (when
in the salt form), acidity when used as the free acid, viscosity
adjustment, prevention of precipitation and clumping, hydrotropic
effects, and increased exhaustibility. The aromatic sulfonic acids
also impart reaction stability, and solubility or emulsification,
as appropriate.
Nonlimiting examples of aromatic sulfonic acids include xylene
sulfonic acid, toluene sulfonic acid, benzene sulfonic acid, cumene
sulfonic acid, dodecylbenzene sulfonic acid, dodecyl diphenyloxide
disulfonic acid, sulfonated dihydroxydiphenylsulfone (sulfonated
DDS), naphthalene sulfonic acid, benzaldehyde sulfonic acid,
methylnaphthalene sulfonic acid, trimethylbenzenesulfonic acid,
aminobenzene sulfonic acid, halobenzenesulfonic acid,
alkoxybenzenesulfonic acid, benzophenone sulfonic acid,
benzophenone disulfonic acid, halonaphthalene sulfonic acid,
alkylnaphthalene sulfonic acid, alkoxynaphthalene sulfonic acid,
carboxybenzene sulfonic acid (3-sulfobenzoic acid),
hydroxybenzenesulfonic acid, hydroxynapthalenesulfonic acid,
carboxymethylbenzene sulfonic acid, alkylbenzene disulfonic acid,
dicarboxybenzene sulfonic acid, acetamidobenzene sulfonic acid,
acetaminonaphthalene sulfonic acid, naphthalene disulfonic acid,
alkyl naphthalene disulfonic acid, dialkylbenzene disulfonic acid,
biphenyl-4,4'-disulfonic acid, benzene and naphthalene sulfonic
acids that contain combinations of halo, alkyl, hydroxy, carboxy,
alkoxy, and acetamino groups, as well as the salts of all of these
compounds. Preferred salt cations are sodium, potassium, and
ammonium. Examples of aromatic sulfonic acid salts include sodium
xylene sulfonate, ammonium xylene sulfonate, sodium toluene
sulfonate, sodium cumene sulfonate, ammonium cumene sulfonate,
potassium toluene sulfonate, potassium cumene sulfonate, and
potassium xylene sulfonate.
The choice of aromatic sulfonic acid to be included in the acrylic
acid polymerization reaction will be determined by a variety of
factors, including aqueous or organic solubility, degree of
sulfonation, viscosity, solidification temperature, and pH. One of
skill in the art will know how to select the appropriate aromatic
sulfonic acid based on known properties of these compounds.
Mixtures of sulfonated aromatic compounds, including salts, can be
used to attain the desired properties. Diphenyl esters or diphenyl
oxide disulfonates are preferred for use in levelers. Xylene
sulfonic acids are preferred for use in exhaustible acids.
Dodecylbenzene sulfonic acids are preferred for use in shampoos and
detergents.
III. Textile Processing or Cleansing Compounds
A wide variety of textile processing and cleansing compounds can be
included in the acrylic acid polymerization reaction to improve the
properties of the polymeric composition. Examples of the families
of chemicals that can be included are described in more detail
below.
A. Surfactants
As noted above, polymers prepared by the polymerization of acrylic
acid in the presence of an aromatic sulfonic acid and a surfactant
can be used in a wide variety of applications, including as acid
dye levelers, pH adjusters, in shampoos and detergents, as
defoamers, yarn lubricants, and in metal cleaners and coatings. The
polymer can be exhausted onto fibers with terminal protonated amino
groups, such as nylon, during textile treatment processes, to
reduce the concentration of the polymeric material in the
wastewater, thereby reducing the B.O.D. and C.O.D. (biological
oxygen demand and carbon oxygen demand, respectively) of the
effluent.
Surfactants contain both a hydrophobic (or lyophobic) end and a
hydrophilic (or lyophilic) end. Surfactants are typically
characterized by the nature of its hydrophilic portion. Anionic
surfactants have a negatively charged moiety in the hydrophilic end
of the molecule, such as a carboxylate or sulfonate salt. Cationic
surfactants have a positive charge in the hydrophilic portion of
the molecule, provided by, for example, an ammonium salt or a
quaternary amine. A zwitterionic surfactant has both positive and
negative charges in the hydrophilic portion. Examples of
zwitterions are long chain amino acids and sulfobetaines. Nonionic
surfactants do not have a formalized charge. Examples include the
monoglycerides of long chain fatty acids and polyoxyethylenated
alkyl phenol.
The hydrophobic end of the surfactant can include a wide variety of
structures, for example, straight or branched long chain alkyl
groups, long chain alkyl benzenes, alkyl naphthalenes, rosins, high
molecular weight propylene oxide polymers, long chain
perfluoroalkyl groups, polysiloxane groups and lignin derivatives.
In general, as the length of the hydrophobic group increases,
solubility in polar or ionic solvents decreases. Branching and
unsaturation typically increases the solubility of the surfactant
in all solvents. Aromatic nuclei increase adsorption onto polar
surfaces. Polyoxypropylene chains also increase adsorption onto
polar surfaces, and increase solubility in organic solvents.
Perfluoroalkyl and polysiloxane moieties are hydrophobic groups
that reduce the surface tension of water to lower values than those
attainable with a hydrocarbon-based hydrophobic group.
Perfluoroalkyl surfaces are both water and hydrocarbon
repellent.
The characteristics of surfactants and their applicability for a
wide variety of applications are described by Rosen in Surfactants
and Interfacial Phenomena, 2nd Edition (John Wiley and Sons, NY),
incorporated herein by reference. In general, the desired chemical
structures of the hydrophilic and hydrophobic portions of the
surfactant will vary with the nature of the solvent and the
conditions of use. As discussed by Rosen, in a highly polar solvent
such as water, the hydrophobic group can be, for example, a
hydrocarbon, fluorocarbon or siloxane chain of proper length,
whereas in a less polar solvent such as an alcohol, a very nonpolar
moiety is required in the hydrophobic part of the surfactant. If a
surface is to be made hydrophobic by the use of a surfactant, a
cationic surfactant is usually preferred. If a surface is to be
made hydrophilic, in general, then anionic surfactants should be
considered. Nonionic surfactants adsorb onto surfaces with either
the hydrophilic or hydrophobic group oriented toward the surface,
depending on the nature of the surface.
It is important to understand that surfactant activity in a
particular system is highly dependent on the nature of the two
immiscible materials. The surfactant must have a chemical structure
that is amphipatic in that solvent system. Methods to select and
manipulate the surfactant for a given system are well known to
those of skill in the art, and are described in a large number of
textbooks, for example, Surfactants and Interfacial Phenomena.
Families of surfactants are also well known to those skilled in the
art, and can be used with the polymers described herein. Common
ionic surfactant families include sodium and potassium salts of
straight chain fatty acids (soaps), sodium and potassium salts of
coconut oil fatty acids, sodium and potassium salts of tall oil
acids, amine salts, acylated polypeptides, linear alkylbenzene
sulfonates, higher alkyl benzene sulfonates, aromatic sulfonates,
petroleum sulfonates, paraffin sulfonates (secondary
n-alkanesulfonates), olefin sulfonates, sulfosuccinate esters,
alkylnaphthylsulfonates, isethioates, sulfuric acid ester salts,
including sulfated linear primary alcohols, sulfated
polyoxyethylenated straight chain alcohols, sulfated triglyceride
oils, phosphoric and polyphosphoric acid esters, perfluorinated
anionics, long chain amines and their salts, diamines and
polyamines and their salts, quaternary ammonium salts,
polyoxyethylenated long-chain amines, quaternized
polyoxyethylenated long chain amines, and amine oxides.
Common nonionic surfactants include polyoxyethylenated
alkylphenols, alkyl phenol ethoxylates (such as the
polyoxyethylenated derivatives of nonylphenol, octyl phenol, and
dodecylphenol), alcohol ethoxylates, polyethylenated polypropylene
glycols, polyoxyethylenated polyoxypropylene glycol,
polyoxyethylenated mercaptans, long chain carboxylic acid esters,
glycerol and polyglycerol esters of natural fatty acids, propylene
glycol, sorbitol, and polyoxyethylenated sorbitol esters,
polyoxyethylene glycol esters and polyoxyethylenated fatty acids,
alkanolamine condensates, alkanolamides, alkanolamine fatty acid
condensates, tertiary acetylenic glycols, polyoxyethylenated
silicones, N-alkylpyrrolidones, and alkylpolyglycosides.
Common zwitterionic surfactants include
.beta.-N-alkylaminopropionic acid, N-alkyl-.beta.-iminodipropionic
acids, imidazolidine carboxylates, N-alkylbetaines, amine oxides,
sulfobetaines and sultaines.
Preferred surfactants include polyethylene glycols, phenol
ethoxylates, ethoxylated alcohols, and phosphoric acid esters.
These families of compounds are discussed in more detail below.
1. Ethylene Glycol Esters and Polyethylene Glycols
Ethylene glycol esters, ethylene glycols and polyethylene glycols
can be used in the preparation of acrylic acid resins to be used as
surfactants, emulsifiers, and lubricants (i.e., detergent
builders).
Ethylene glycol can be in the form of a mono or diester, for
example, ethylene glycol monomethyl ether, ethylene glycol dimethyl
ether, ethylene glycol monoethyl ether, ethylene glycol diethyl
ether, ethylene glycol (mono or di)-isopropyl ether, ethylene
glycol (mono or di)-n-propyl ether, ethylene glycol (mono or
di)-n-butyl ether, ethylene glycol (mono or di)-sec-butyl ether,
and ethylene glycol (mono or di)-isobutyl ether. Also appropriate
are the mono- and di- alkyl ethers of diethylene glycol.
Polyethylene glycols (referred to as "PEG") can be purchased from
any of several commercial sources in molecular weights ranging from
100 to 6,000. Polypropylene glycols are also available from a
number of sources.
2. Phenol Ethoxylates
Long chain alkyl phenol ethoxylates are known surfactants. These
compounds can be added to the acrylic acid polymerization reaction
to form a polymer that can be used as an exhaustible surfactant or
emulsifier, exhaustible acid dye leveler, liquid laundry detergent,
or liquid detergent additive. A commonly used phenol ethoxylate is
nonylphenol ethoxylate, which is commercially available having a
wide range of ethoxylation, including 4 mole, 6 mole, 9 mole, 15
mole, and 30 mole. All of these are suitable for incorporation into
the acrylic acid resins. Various types of ethoxylated octylphenol
and dodecylphenol are also commercially available. Combinations of
long chain alkyl phenol ethoxylates are also suitable.
The greater the extent of ethoxylation of the long chain phenol
ethoxylate, the higher its water solubility. Therefore, phenol
ethoxylates with high ethoxylation values should be used in the
acrylic acid polymerization reaction when a product is desired that
has high wettability or aqueous solubility. In contrast, a phenol
ethoxylate with a low ethoxylation value should be used to prepare
a product with low solubility and high exhaustibility. For example,
a nonyl phenol with a low extent of ethoxylation is suitable for
inclusion in a product used as a defoamer, in which low solubility
is an important factor.
3. Ethoxylated Alcohols
Ethoxylated alcohols can be included in the acrylic acid
polymerization process to provide a product that is useful as a
surfactant, emulsifier, low foam detergent or wetting agent.
Preferred compounds are ethoxylated decyl alcohol and tridecyl
alcohol. These compounds are commercially available with
ethoxylation values of approximately 4 mole, 6 mole, 8.5 mole, 9
mole, 12 mole, 15 mole, and 30 mole. Decyl alcohols are preferred
for use as low temperature surfactants and tridecyl alcohols are
preferred for use as high temperature surfactants.
B. Perfluoroalkylethyl and Perfluorinated Alcohols
A perfluoroalkylethyl alcohol can be included as desired in the
reaction mixture. Perfluoroalkylethyl and perfluorinated alcohols
assist in the solubilization of perfluoroalkylethyl acrylates and
methacrylates in the reaction mixture. They can also act as chain
terminating agents in the polymerization reaction. An example of a
perfluoroalkylethyl alcohol is HOCH.sub.2 CH.sub.2 R.sub.f, wherein
R.sub.f is (CF.sub.2 CF.sub.2).sub.n CF.sub.2 CF.sub.3, and n is
1-7. This class of alcohols is often bought as a mixture of R.sub.f
values. A preferred mix is approximately 40% n=2, approximately 30%
n=3, approximately 20% n=4, approximately 10% n=5, and little n=1,
6, and 7. In an alternative embodiment, additional nonfluorinated
alkyl carbons, or alternatively, polyoxyalkylene, can be placed
between the hydroxyl function and R.sub.f, e.g., HOCH.sub.2
(CF.sub.2 CF.sub.2).sub.n CF.sub.2 CF.sub.3, HOCH.sub.2 CH.sub.2
CH.sub.2 (CF.sub.2 CF.sub.2).sub.n CF.sub.2 CF.sub.3, HOCH.sub.2
CH.sub.2 CH.sub.2 CH.sub.2 (CF.sub.2 CF.sub.2).sub.n CF.sub.2
CF.sub.3, and HOCF.sub.2 CF.sub.2 (CF.sub.2 CF.sub.2).sub.n
--CH.sub.2 CH.sub.2 CH.sub.2 O--(CH.sub.2 CH.sub.2 O).sub.m (H or
alkyl).
Suitable perfluorinated alcohols are also of the formula CF.sub.3
(CF.sub.2).sub.q OH, wherein q is 1-11, and also hexafluorobutyl
and tetrafluoropropyl alcohol.
C. Perfluoroalkylethyl Amines
A perfluoroalkylethyl amine can also be included in the reaction
mixture as desired. An example of a perfluoroalkylethyl amine is
H.sub.2 NCH.sub.2 CH.sub.2 R.sub.f, wherein R.sub.f is CF.sub.2
CF.sub.2).sub.n CF.sub.2 CF.sub.3, and n is 1-7. This class of
amines is often bought as a mixture of R.sub.f values. A preferred
mix is approximately 40% n=2, approximately 30% n=3, approximately
20% n=4, approximately 10% n=5, and little n=1, 6, and 7. In an
alternative embodiment, additional nonfluorinated alkyl carbons, or
alternatively, polyoxyalkylene, can be placed between the amine
function and R.sub.f, e.g., H.sub.2 NCH.sub.2 (CF.sub.2
CF.sub.2).sub.n CF.sub.2 CF.sub.3, H.sub.2 NCH.sub.2 CH.sub.2
CH.sub.2 (CF.sub.2 CF.sub.2).sub.n CF.sub.2 CF.sub.3, H.sub.2
NCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 (CF.sub.2 CF.sub.2).sub.n
CF.sub.2 CF.sub.3, and H.sub.2 NCF.sub.2 CF.sub.2 (CF.sub.2
CF.sub.2).sub.n --CH.sub.2 CH.sub.2 CH.sub.2 O--(CH.sub.2 CH.sub.2
O).sub.m (H or alkyl).
D. Phosphoric Acid Derivatives
Phosphoric acid and its salts, as well as phosphoric acid esters
and their salts, can be included in the acrylic acid polymerization
reaction to provide a product that is a superior chelating agent,
flocculant, flame retardant, metal cleaner, anti-static agent,
emulsifying agent (for example, in pesticides, herbicides, and in
liquid fertilizer), dry cleaning solution, or hydrotrope. Preferred
phosphoric acid esters are phosphated polyoxyethylenated alcohols
(acid or salt), phosphated polyoxyethylenated phenols (acid or
salt), and sodium alkyl phosphates. A preferred phosphoric acid
ester is 2-ethylhexyl phosphoric acid. Any cation can be used to
form the salt, including sodium, potassium, ammonium, substituted
ammonium, and quaternary amine. Other suitable phosphoric acid
esters include phosphated decyl alcohol with ethoxylation values of
4 and 6 mole for use as flame retardants and antistatic agents.
E. Ultra-Violet Absorbing Agents
Ultra-violet absorbing agents can be included in the acrylic acid
polymerization reaction to provide a product that provides a
protective coating against ultra-violet radiation. Any aromatic
ultra-violet absorbing molecule is suitable. Examples include
2,4-dihydroxy-benzophenone (Uvinol.TM.-400, BASF Corporation),
2-hydroxy-4-methoxy-benzophenone (Uvinol.TM. M-40, BASF
Corporation), 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (Uvinol.TM.
D-49, BASF Corporation), Uvinol.TM. 490 (BASF Corporation, mixture
of Uvinol.TM. D-49 and other tetrasubstituted benzophenones),
2,2',4,4'-tetrahydroxybenzophenone (Uvinol.TM. D-50),
2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid (Uvinol.TM.
MS-40), disodium
2,2'-dihydroxy-4,4'-dimethoxy-5,5'-disulfobenzophenone (Uvinol.TM.
DS-49), ethyl-2-cyano-3,3-diphenylacrylate (Uvinol.TM. N-35),
2-ethylhexyl-2-cyano-3,3-diphenylacrylate (Uvinol.TM. N-539), and
4-methoxy-5-hydroxy-benzophenone-3-sulfonic acid.
In an alternative embodiment, para-aminobenzoic acid be reacted
with acrylic acid or methacrylic acid to form a (meth) acrylamide,
that is used as a monomer in the polymerization reactions described
herein.
Fluorochemicals are also useful with the polymers described herein.
A number of compositions are commercially available and known to
those skilled in the art. Fluorochemical coatings have been
developed that prevent wetting of the textile surface, by
minimizing chemical contact between of the textile surface, and
substances that can stain the textile, making the substance easier
to remove. Typical fluorochemicals contain a perfluoroalkyl radical
having three to twenty carbons, and are produced by condensation of
a fluorinated alcohol or fluorinated primary amine with a suitable
anhydride or isocyanate, for example, N-ethyl
perfluorooctyl-sulfonamidoethanol and toluene diisocyanate reacted
in a 2:1 molar ratio.
Examples of commercially available fluorochemical coatings include
Scotchgard.TM. 358 and 351 (Minnesota Mining & Mfg. Co.) and
Teflon.TM. (E. I. DuPont Nemours & Co.). U.S. Pat. No.
4,518,649 to Wang, et al., discloses releasing finishes for
textiles. A number of water and soil repellents for fabrics are
reviewed by Sodano in Chemical Technology Review No. 134, Noyes
Data Corporation, Park Ridge, N.J. 1979. European patent
application by Allied Corporation describes an oil and soil
repellent finish based on a mixture of a quaternary ammonium salt
containing trialkyl dodecyl ammonium anion and cocoatrialkyl
ammonium anion and a fluorochemical consisting of
polycarboxybenzene esterified with fluorinated alcohols. British
patent numbers 1,379,926 and 1,405,268 to Ciba-Geigy report several
fluorocarbons useful for treatment of fibers to increase oil and
water resistance.
F. Examples of Combinations of Reaction Components.
A wide variety of textile processing agents can be prepared by
polymerizing H.sub.2 C.dbd.CHCO.sub.2 X, H.sub.2 C.dbd.CR.sup.1
CO.sub.2 X, HR.sup.2 C.dbd.CHCO.sub.2 X, HR.sup.2 C.dbd.CR.sup.1
CO.sub.2 X, HR.sup.2 C.dbd.CHCOX, H.sub.2 C.dbd.CHCOX, H.sub.2
C.dbd.CR.sup.1 COX, HR.sup.2 C.dbd.CR.sup.1 COX, H.sub.2
C.dbd.CHCSO.sub.v X, HR.sup.2 C.dbd.CHCSO.sub.v X, HR.sup.2
C.dbd.CR.sup.1 CSO.sub.v X, H.sub.2 C.dbd.CR.sup.1 CSO.sub.v X,
H.sub.2 C.dbd.CHCON(R.sup.3).sub.2, HR.sup.2
C.dbd.CHCON(R.sup.3).sub.2, H.sub.2 C.dbd.CR.sup.1
CON(R.sup.3).sub.2, or HR.sup.2 C.dbd.CR.sup.1 CON(R.sup.3).sub.2,
or a combination thereof, in the presence of an aromatic sulfonic
acid or its salt, and optionally, one or more of the textile
processing compound described above. All of these variations are
intended to fall within the scope of the invention. Nonlimiting
general examples of a few illustrative combinations of reactants
are provided below.
Composition A
Component 1. perfluoroalkylethyl acrylate or methacrylate, or a
mixture thereof, perfluoroalkylethylamidoacrylate or methacrylate,
or perfluoroalkylethylsulfonyl aminopropenoate;
Component 2. perfluoroalkylethyl alcohol, perfluoroalkylethylamine,
perfluoroalkylsulfate, perfluoroalkylethoxylate, or
perfluoroalkylphosphate;
Component 3. alkyl acrylate, alkyl methacrylate, aryl acrylate,
aryl methacrylate, alkaryl acrylate, or alkaryl methacrylate, or a
mixture thereof;
Component 4. H.sub.2 C.dbd.CHCO.sub.2 X or H.sub.2 C.dbd.CR.sup.1
CO.sub.2 X;
Component 5. aromatic sulfonic acid, for example aryl sulfonate,
alkaryl sulfonate, or alkyl diphenyloxide sulfonate, alkyl
sulfonate, alkylethoxy sulfate, or sodium lauryl ether sulfate;
Component 6. polymerization initiator; and
Component 7. water.
Composition B
Component 1. perfluoroalkylethylacrylates or methacrylates or a
mixture thereof (CH.sub.2 .dbd.C[H or CH.sub.3 ] [(C(O)OCH.sub.2
CH.sub.2 R.sub.f ], wherein R.sub.f is CF.sub.3 CF.sub.2 (CF.sub.2
CF.sub.2)n, and n=1-7); perfluoroalkylethyl alcohol (HOCH.sub.2
CH.sub.2 R.sub.f, wherein R.sub.f is CF.sub.2 CF.sub.2).sub.n
CF.sub.2 CF.sub.3, and n is 1-7);
Component 2. acrylic acid or methacrylic acid, or a mixture
thereof;
Component 3. alkylacrylate or methacrylate (CH.sub.2 .dbd.C[H or
CH.sub.3 ] [(C(O)OZ], wherein Z is a polyoxyalkylene, including but
not limited to --(CH.sub.2 CH.sub.2 O).sub.m H, --(CH.sub.2
CH.sub.2 CH.sub.2 O).sub.m H, --(CH.sub.2 CH.sub.2 O).sub.m R, or
--(CH.sub.2 CH.sub.2 CH.sub.2 O).sub.m R wherein m is 1-200);
Component 4. aromatic sulfonic acid;
Component 5. an anionic or nonionic surfactant, or combination
thereof; and,
Component 6. a persulfate initiator in water.
Composition C
To the reaction components in Composition B. is added an acrylic
acid derivative of the formula CH.sub.2 .dbd.C[H or CH.sub.3 ]
[(C(O)OC(R.sup.2).sub.2 R.sup.3 Y], wherein R.sup.3 is alkylene or
polyoxyalkylene, and Y is --SO.sub.3 H, --CO.sub.2 H, or --PO.sub.4
H, or a salt thereof.
Composition D
To the reaction components in Composition B. is added an acrylic
acid derivative of the formula CH.sub.2
.dbd.C(H)C(O)NHC(CH.sub.3).sub.2 CH.sub.2 SO.sub.3.sup.31 Na.sup.+
or CH.sub.2 .dbd.C(CH.sub.3)C(O)NHCH.sub.2 CH.sub.2 CH.sub.2
SO.sub.3.sup.- Na.sup.+.
V. Preparation of the Polymer
The reaction mixture typically contains at least H.sub.2
C.dbd.CHCO.sub.2 X, H.sub.2 C.dbd.CR.sup.1 CO.sub.2 X, HR.sup.2
C.dbd.CHCO.sub.2 X, HR.sup.2 C.dbd.CR.sup.1 CO.sub.2 X, HR.sup.2
C.dbd.CHCOX, H.sub.2 C.dbd.CHCOX, H.sub.2 C.dbd.CR.sup.1 COX,
HR.sup.2 C.dbd.CR.sup.1 COX, H.sub.2 C.dbd.CHCSO.sub.v X, HR.sup.2
C.dbd.CHCSO.sub.v X, HR.sup.2 C.dbd.CR.sup.1 CSO.sub.v X, H.sub.2
C.dbd.CR.sup.1 CSO.sub.v X, H.sub.2 C.dbd.CHCON(R.sup.3).sub.2,
HR.sup.2 C.dbd.CHCON(R.sup.3).sub.2, H.sub.2 C.dbd.CR.sup.1
CON(R.sup.3).sub.2, or HR.sup.2 C.dbd.CR.sup.1 CON(R.sup.3).sub.2,
or a combination thereof, an aromatic sulfonic acid, a free radical
initiating agent, and water. A textile processing or cleansing
chemical as defined above should be added as appropriate to produce
a polymeric composition with the desired characteristics. Any ratio
of components is suitable that provides a product with the desired
properties. One of ordinary skill in the art can easily manipulate
the ratio of components to determine the best mix for a given
application without undue experimentation.
Table 1 provides a typical range of percentages by weight for the
reaction components. It should be understood that these ranges are
not limitations, but exemplary, and superior products for certain
applications can be formulated using the components described
herein at concentrations other than in these ranges.
In a preferred embodiment, the aromatic sulfonic acid is present in
an amount of at least approximately 10% by weight of all of the
reaction components in the reaction mixture (including water).
TABLE 1 ______________________________________ Ranges of Percent
Composition for Polymeric Mixtures of Acrylic Acids and Aromatic
Sulfonic Acids. Percent Composition Component by weight
______________________________________ acrylic acid 15-22 free
radical initiating agent 3-5 water remaining percentage aromatic
sulfonic acid or its salts 10-40 textile processing chemical 0-40
ethylene glycol ester ethylene glycol polyethylene glycol
ethoxylated phenol ethoxylated alcohol phosphoric acid/ester UV
absorbing agents fluorinated alkyl ethyl alcohol and unsaturated
esters, fluorinated alkyl ethyl amine and unsaturated amides
fluorochemicals ______________________________________
In general, as the ratio of sulfonated aromatic compound increases,
the molecular weight of the resulting polymer decreases, since the
sulfonated aromatic compound acts as a chain terminating reagent
for the acrylic acid polymerization. Polymers of lower molecular
weight are desirable for exhaustible textile treatments because
they tend to penetrate the shank of the polyamide fiber more easily
than high molecular weight polymers. Polymers of higher molecular
weight give good exhaustion and high substrate surface
concentration.
Any known free radical initiating agent can be used to initiate the
acrylic acid polymerization reaction, including sodium persulfate,
potassium persulfate, ammonium persulfate, benzoyl peroxide,
hydrogen peroxide, sodium peroxide, acetyl peroxide, lauryl
peroxide, azobisisobutyronitrile, t-butyl peracetate, cumyl
peroxide, t-butyl peroxide, and t-butyl hydroperoxide. Persulfate
initiators increase the water solubility of the polymeric
composition.
The appropriate weight percent of free radical agent to be used in
the polymerization reaction will be a function of the molecular
weight of the initiator. In general, the amount of initiator needed
for polymerization increases as the percent of monomer in the
reaction solution increases. However, in a concentrated reaction
solution, the need to use a substantial amount of initiator must be
balanced against the tendency of high quantities of initiator to
actually decrease molecular weight and viscosity. Typically, the
weight of the initiator used is approximately 15-30% that of the
weight of the monomer, but the optimal amount can be determined in
a given reaction by routine experimentation.
In a preferred embodiment, all reaction components are mixed and
heated to a temperature ranging from approximately 50.degree. C. to
100.degree. C., depending on the temperature required for free
radical generation of the initiator. The initiation of
polymerization is sufficiently exothermic to raise the temperature
of solution to between 100.degree. and 115.degree. C. The heat of
reaction is controlled by reflux. The reaction temperature is
allowed to stabilize, and then maintained at 100.degree. C. for at
least 30 minutes. Preferably, polymerization is allowed to proceed
until one percent or less monomer is left in the reaction solution.
The thickness of the reaction mixture, or tendency to gel, can be
adjusted by increasing the ratio of sulfonated aromatic compound in
the reaction mixture.
Once the reaction is complete, the reacted material is diluted to
the desired solids concentration and viscosity, based on cost of
product, effective concentration, and ease of handling. A wide
variety of viscosity adjusting reagents can be used, including
water and sulfonated aromatic acid or salt solutions. Preferred
viscosity adjusting reagents include water, and the sodium,
potassium, and ammonium salts of xylene sulfonate, cumene
sulfonate, toluene sulfonate, and dodecyldiphenyl disulfonate. The
resulting polymeric solution is acidic. If desired, the pH of the
solution can be adjusted with a base such as ammonium, sodium,
lithium, or potassium hydroxide, or amines such as triethanolamine.
The reaction can be performed in one batch or by dose feed. In a
dose feed process, the reaction is started by adding a percentage
of the starting material to the reactor, and heating to initiate
reaction. After the reaction creates an exotherm, additional
reactants are added. The dose feed process can be used to control
the vigorous nature of the reaction. As an example, one-third to
one-half of the starting materials is added to the reactor. After
the solution boils, one-third of the remaining material is added.
The final two-thirds of the remaining material is added in at a
rate so as not to reduce the reaction temperature below the
initiation temperature.
V. Application and Use of the Polymer
The following examples provide representative formulations for a
wide variety of textile applications. The ratios of reactants in
these formulations can be modified as necessary by one skilled in
the art to optimize a product for a specific use. Other components
can also be added as required without altering the scope of the
polymeric composition described herein. These formulations are
merely illustrative of the types of products that can be prepared
by using the method described herein, and are not intended to limit
the scope of the invention. All percentages are by weight unless
otherwise specified.
EXAMPLE 1
Preparation of a Tanning Agent for Leather
A superior tanning agent for leather was prepared by blending and
reacting, in order:
______________________________________ Water 38.0% Sodium Xylene
Sulfonate 30.0% Xylene Sulfonic Acid 10.0% Ammonium Persulfate 4.0%
Methacrylic Acid 18.0% ______________________________________
The product mixture had an active solids content of approximately
39%. The product was diluted to approximately 20% active solids
before use with a mixture of water and sodium xylene sulfonate.
EXAMPLE 2
Preparation of a Surfactant
An exhaustible surfactant was prepared by blending and
reacting:
______________________________________ Methacrylic acid 15.0%
Sodium cumene sulfonate 30.0% Ammonium persulfate 5.0% Nonyl phenol
ethoxylated (9 mole) 20.0% Water 30.0%
______________________________________
The product had an active solids content of approximately 51%. It
was diluted to a 45% active solids content with sodium cumene
sulfonate and water.
EXAMPLE 3
Preparation of an Exhaustible Acid
An exhaustible acid was prepared by blending and reacting:
______________________________________ Methacrylic Acid Monomer
22.0% Xylene sulfonic acid 33.0% Ammonium persulfate 3.0% water
62.0% ______________________________________
The product had an active solids content of approximately 55%. It
was diluted before use to a 35.5% active solids content with water
and sulfamic acid.
EXAMPLE 4
Preparation of an Exhaustible Acid
An alternative formulation for an exhaustible acid is:
______________________________________ Methacrylic Acid Monomer
16.0% Xylene sulfonic acid 20.0% Ammonium persulfate 4.0% Water
60.0% ______________________________________
The reaction was performed as described in Example 3. The reacted
product was diluted with 2:1 water to xylene sulfonic acid.
EXAMPLE 5
Preparation of an Exhaustible Acid
An alternative formulation for an exhaustible acid is:
______________________________________ Methacrylic Acid Monomer
28.0% Xylene sulfonic acid 30.0% Ammonium persulfate 5.0% Water
37.0% ______________________________________
The reaction was performed as described in Example 3. 500 ml of
product solution was diluted to 748 ml by the addition of 200 ml of
water and 30 grams of powdered sulfamic acid. To this was added 18
ml of dodecylbenzenesulfonic acid to form the final product.
EXAMPLE 6
Preparation of an Exhaustible Shampoo
An exhaustible shampoo that does not diminish the soil and stain
characteristics of nylon carpets was prepared by reacting:
______________________________________ Methacrylic acid 12.5%
Acrylic Acid 12.5% Xylene sulfonic acid 8.0% Sodium xylene
sulfonate 17.5% Ammonium persulfate 3.0% Isopropyl alcohol 4.5%
Water 21.5% Sodium dodecyl benzene sulfonate 20.5% 100.0% Dilution
& Neutralization Reaction Product 62.5% Sodium xylene sulfonate
13.5% Water 17.0% NaOH 50% 7.0% 100.0%
______________________________________
Final product 38% solids, and pH 5.
EXAMPLE 7
Preparation of a Powder or Liquid Detergent
A powder or liquid laundry detergent or builder was prepared by
reacting a mixture of:
______________________________________ Acrylic acid 18% Xylene
sulfonic acid 5% Ammonium Persulfate 4% Sodium cumene sulfonate 23%
Water 30% Nonylphenol (9 mole ethoxylate) 20% 100%
______________________________________
The product is spray dried to be used as a powder or used as is in
the liquid state as a liquid laundry product. The product functions
as both a detergent and a detergent builder. It can also serve the
function of surfactant, hydrotrope, soil absorber, or redeposition
agent.
EXAMPLE 8
Preparation of a Hard Plastic Material
A hard plastic material is prepared by mixing and heating to
80.degree. C. all of the components listed in Formulation A or B
below except methacrylic acid, and then adding the methacrylic acid
to the heated components. After the reaction is completed and the
water is driven off, the product can be hot pressed or molded to a
desired shape. Methyl methacrylate, acrylic acid, or another
acrylic acid derivative described in Section II, can be substituted
for methacrylic acid.
______________________________________ Formulation A: Ammonium
Persulfate 3% Methacrylate acid 18% Xylene Sulfonic Acid 5% Sodium
Xylene Sulfonate 10% Phosphoric Acid (75%) 20% Water 44% 100%
Formulation B: Ammonium Persulfate 3% Methacrylate acid 18% Xylene
Sulfonic Acid 5% Sodium Xylene Sulfonate 10% Sulfamic Acid (powder)
20% Water 44% 100% ______________________________________
EXAMPLE 9
Preparation of an Exhaustible Surfactant or Acid Dye Leveler
An acrylic acid resin that is useful as an exhaustible surfactant
or exhaustible acid dye leveler was prepared by reacting:
______________________________________ Water 30% Sodium cumene
sulfonate (45%) 30% Nonyl phenol (9 M) 20% Methacrylate acid 15%
Ammonium Persulfate 5% 100%
______________________________________
The product made from this formulation had a solids content of
approximately 51%. The solids content was diluted to approximately
45% with water. This product can be used instead of standard
wetting agents and dye levelers in textile applications to reduce
the B.O.D. and C.O.D. of the wastewater. It can also be used as a
surfactant for liquid laundry detergent and dishwashing detergents,
as well as an emulsifying agent for yarn lubricants. The product
forms a stable emulsion when poured in water at a pH from pH 4.3 to
pH 12. This formulation can also be used as an industrial wetting
agent for synthetic and natural fibers, particularly cotton.
EXAMPLE 10
Preparation of an Acid Dye Leveler
An acid dye leveler was prepared by reacting:
______________________________________ Sodium cumene sulfonate
(40%) 60% Isopropyl alcohol 7% Dodecyl diphenyloxide disulfonate
10% Methacrylate acid 15% Xylene sulfonic acid 4% Ammonium
persulfate 4% 100% ______________________________________
500 milliters of the reaction mixture was diluted to 640 ml with
water to provide the final product.
EXAMPLE 11
Preparation of a Yarn Lubricant
A yarn lubricant was prepared by reacting:
______________________________________ Methacrylate acid 15%
Hydrogen peroxide (35%) 6% Water 54% Polyethylene glycol 400 20%
Xylene sulfonate acid 5% 100%
______________________________________
EXAMPLE 12
Preparation of a Copolymerizing Solution
A copolymerizing solution is prepared using the stain resistant
composition described in U.S. Pat. No. 5,061,763, which is the
reaction product of methacrylic acid and the formaldehyde
condensation polymer of sodium naphthalene sulfonate and
4,4'-dihydroxydiphenylsulfone. Glacial methacylic acid (99% in
water, 22.3 grams), water (48.7 grams), formaldehyde condensation
polymer of sodium naphthalene sulfonate and
4,4'-dihydroxydiphenylsulfone (Erinal.TM. NW-LQ; 37-40% solution;
12.3 grams), potassium persulfate (5.7 grams), and sodium xylene
sulfonate (40% solution; 11.0 grams) were placed in a two liter
round bottom flask equipped with a mechanical stirrer, reflux
condenser, thermometer, and water bath. The brownish solution was
heated to 65.degree. C. with stirring. A large exothermic reaction
rapidly raised the temperature of the reaction mixture to
100.degree. C. The temperature was maintained at
90.degree.-100.degree. C. for 30 minutes. The resulting viscous,
yellow/red solution was diluted with water to give a final total
solids concentration of 32 weight percent.
The reaction product (20%) was reacted with:
______________________________________ Methyl Methacrylate monomers
15% Hydrogen peroxide (35%) 6% Water 54% Xylene sulfonate acid 5%
______________________________________
The vessel was charged with water, xylene sulfonic acid, the 32%
composition, the methyl methacrylate monomers, heat to 50.degree.
C. and add hydrogen peroxide. The temperature was raised to
100.degree.-105.degree. C. and run 30 minutes. Water was added to
gain desired solids level.
The product is useful as a textile coating, resin curing agent, and
paint additive.
EXAMPLE 13
Preparation of a Defoamer
A defoamer is prepared by reacting:
______________________________________ Methacrylate or acrylic acid
12% Water 43% Benzoyl peroxide 5% Nonyl phenol 1-5 mole (EO) 40%
100% ______________________________________
EXAMPLE 14
Preparation of a Chelating Agent
A chelating agent is prepared by reacting:
______________________________________ Acrylic acid monomer 15%
nitryl triacetic acid 15% sodium phosphate 15% Ammonium persulfate
3% Water 52% 100% ______________________________________
Product can be partially neutralized with diethylamine or
triethylamine to pH 5, or more amine can be added to get to pH
8.
EXAMPLE 15
Preparation of a Flocculant
A flocculant is prepared by reacting:
______________________________________ Acrylic acid monomer 18%
Xylene sulfonic acid 5% Ammonium persulfate 3% Water 74% 100%
______________________________________
Product can be added to a waste stream in the presence of aluminum
sulfate to form a bond with positively charged ions to form a
precipitant mass for sludge press removal.
EXAMPLE 16
Preparation of an Anti-static Agent
An anti-static agent is prepared by reacting:
______________________________________ Methacrylic Acid 15% Sodium
xylene sulfonate 20% Xylene sulfonic acid 5% Phosphated
2-ethylhexanol 20% Ammonium persulfate 3% Water 37% 100%
______________________________________
The product can be used as an after treatment agent for textile
fabrics and nylon carpets. The product can also be used as a
component in nylon yarn manufacturing as a lubricant additive for
static control.
EXAMPLE 17
Preparation of a Flame Retardant
A flame retardant is prepared by reacting:
______________________________________ Methacrylic Acid 18% Sodium
xylene sulfonate 25% Ammonium persulfate 4% Ammonium sulfamate 15%
Naphthalene sulfonic acid condensate 10% Water 28% 100%
______________________________________
The product can be used on nylon and cotton, in exhaust after treat
cycles, and spray dried on all other fabrics in small quantities
for flame retardation.
EXAMPLE 18
Preparation of a Metal Cleaner
A metal cleaner is prepared by reacting:
______________________________________ Acrylic acid monomer 15%
Xylene sulfonic acid 5% Sodium xylene sulfonate 15% Ethylene glycol
2% Benzene sulfonic acid 10% Sodium phosphate 5% Water 48% 100%
______________________________________
EXAMPLE 19
Preparation of a Metal Coating
A metal coating is prepared by reacting:
______________________________________ Methyl methacrylic 5%
Methacrylic acid monomer 10% Acrylic acid monomer 5% Xylene
sulfonic acid 5% Sodium xylene sulfonate 10% Fluoropolymer
(Zonyl.TM. 5180, Du Pont) 10% Water 55% 100%
______________________________________
and diluting the reaction product to 60% by blending with 20%
isopropyl alcohol and 20% ammonium thiocyanate (50% solution).
Spray on metal for quick drying protective coating.
Unless specified otherwise, the processes described in the Examples
above used the following reaction process, adding the reaction
components as follows: water, individual components, then monomer
acid, then initiator. The temperature of the vessel was raised to
65.degree.-70.degree. C., and then heat removed. After exotherm,
the reaction was allowed to proceed for 30 minutes. Final
adjustments were made with water or hydrotrope to the desired
solids level, and base added to the desired pH value.
Although all examples were performed in a batch process, continuous
methods can also be used. Surfactants can also be incorporated for
use in the emulsion processes.
EXAMPLE 20
Preparation of an Exhaustible Soil Resist Agent
Exhaustible soil resist agents were prepared with the components by
weight percent as indicated below. The perfluoroalkylethyl alcohol
was supplied by Atochem North America Fluorochemicals Division
(Foralkyl EOH 6 NL, R.sub.f =6, 8, 10 and 12). Another suitable
perfluoroalkylethyl alcohol is Fluowet EA 93 (Hoechst Corporation).
The perfluoroalkylethylmethacrylate was obtained by esterifying
methacrylic anhydride with the perfluoroalkylethyl alcohol,
followed by rinsing the product with mild NaOH.
The reactants were blended together, and the pH was adjusted to
approximately 4 with 15% NaOH. The mixture was rapidly stirred and
heated to 70.degree.-80.degree. C. for 30 minutes. The resulting
product is useful as a soil resist agent and oil and water
repellent for both hard and soft surfaces. The product can be
applied to fabrics and other surfaces by conventional application
techniques which include spraying, foaming, padding, kiss rolling,
flooding, long bath exhaustion, etc.
______________________________________ 1 2
______________________________________
Perfluoroalkylethylmethacrylates 13.5 13.5
Perfluoroalkylethylalcohols 2.7 2.7 Methacrylates Acid 1.4 1.4
2-Ethylhexylmethacrylate 1.4 1.4 Sodium Xylenesulfonate - 40% 40.5
40.5 Sodium Dodecylbenzene Sulfonate - 40% 2.7 2.7 Sodium
Persulfate 4.0 1.4 Water 33.8 30.0 Sodium
2-acrylamido-2-methylpropane 0 6.4 sulfonate - 50% 100.0 100.0
______________________________________
EXAMPLE 21
Preparation of a Surfactant for Continuous Dying of Nylon Fiber
The reactor vessel was charged, in order, as follows: 58.13%
polyoxyethylene tridecyl ether (9 mole, 80%) (CAS 24938-91-8);
12.10% methacrylic acid; 8.00% 2-ethyl hexanol; 15.00% xylene
sulfonic acid (90%); 3.00% ammonium persulfate; and 3.77%
water.
After charging, the vessel was heated under reflux at
105.degree.-110.degree. C. for one and a half hours, and then
cooled to 80.degree. C. After cooling to 80.degree. C., the
reaction product was diluted and neutralized as follows: 56.0%
reaction Product; 14.0% sodium xylene sulfonate (40%); 23.0% water;
and 7.0% triethanolamine (85%).
Modifications and variations of the present invention, new acrylic
acid derivatives and their method of use, will be obvious to those
skilled in the art from the foregoing detailed description of the
invention. Such modifications and variations are intended to come
within the scope of the appended claims.
* * * * *